Application of cumylphenol and derivatives thereof in plastic compositions

ABSTRACT

Cumylphenol and its ester derivatives may be used as accelerators in amine-cured epoxy systems. Also, cumylphenol and its derivatives have been discovered to be useful as reactive diluents for epoxy, phenol and urethane resins. The glycidyl ether, a new composition of matter, is also useful as a reactive diluent for urethane resins. Additionally, the ester derivatives are non-reactive plasticizers for urethane and the benzoate and higher acyl ester for rigid polyvinyl chloride. The benzoate and higher acyl esters are also new compositions.

This is a division of application Ser. No. 672,425, filed Mar. 31, 1976,now U.S. Pat. No. 4,102,862, issued July 25, 1978.

This invention relates to the use of cumylphenol and derivatives thereofas accelerators, reactive diluents and non-reactive plasticizers.

More specifically, this invention teaches the use of cumylphenol,admixtures thereof (particularly with alpah-methylstyrene dimer) andcumylphenyl esters as a replacement for nonylphenol and dinonylphenolsas accelerators for amine-cured epoxy resins. The use of thenonylphenols as accelerators is well known and is described in U.S. Pat.Nos. 3,637,902; 3,740,373; and 3,763,102. It has been found that thecumylphenol per se is a much more effective accelerator than nonylphenoland that the mixture thereof with alpha-methylstyrene dimer provides alow-cost accelerator useful for controlling cure rates and improving theimpact resistance of the resultant epoxide composition. Admixtures ofcumylphenol and alpha-methylstyrene dimer may be readily obtained as aby-product from the commercially used process for making cumene fromphenol. In this process, this by-product appears as a bottoms product inthe purification of the cumeme along with other high molecular weightproducts. The desired admixture may be separated by conventional vacuumdistillation of the bottoms or the bottoms may be used directly withoutpurification.

In another embodiment of the invention, cumylphenol and derivativesthereof have been found useful as reactive diluents for epoxy, furan andphenolic resins. The glycidyl ether derivatives may also serve thisfunction for urethane resins. These ethers are new compositions ofmatter and provide a low cost replacement for conventionally employedco-monomeric materials. In certain instances, their use improves thechemical and physical properties of the cured resins.

In still another embodiment of the invention, it has been found thatesters of cumylphenol are useful as non-reactive plasticizers forpolyurethanes. The benzoate and the higher acyl esters, which are uniquecompounds, may be used for rigid polyvinyl chloride. Here again the costof the finished resin may be markedly reduced.

The derivatives of cumylphenol which are useful in the invention may berepresented by the following formula: ##STR1## where R is an acyl group,##STR2## where R' is an alkyl, aryl, or aralkyl group having 1 to 12carbon atoms, or a glycidyl group having 3 to 6 carbon atoms. Mostpreferably, R' is a methyl, an ethyl, or a long chain alkyl group, andthe glycidyl group is ##STR3## Certain of these compounds are well knownin the art. The acetyl derivative is described by Tsivunin et al., Biol.Akliv. Soldin. 1968, 172-5 (Russ.). However, some are new compositionsof matter, viz., the glycidyl ether, the benzoate ester and the higheracyl esters of cumylphenol. Of this latter group, the most important arethe esters where R' has from 6 to 10 carbon atoms.

Where the cumylphenol or its esters are used as accelerators foramine-cured epoxy systems, the amount of the cumylphenol materials mayrange from 5 to 30%, preferably from 10 to 20%, based on the weight ofresin to be cured. Any of the conventional amine-curing systems may beused, e.g., aliphatic polyamines, aromatic polyamines andpolyaminoamide.

In this application, the epoxy resin in the liquid state is placed in areactor and mixed with the amine-curing system. Generally from 5 to 50parts of curative are used along with the cumylphenol accelerator. Thereaction mass is heated to a temperature in the range of from 0° to 250°C. at pressures from 10 mm Hg to 5 atm. until the desired cure isachieved.

Where the cumylphenol derivatives are used as reactive diluents, theymay be present in from about 10 to about 200 parts per 100 parts of theresin, preferably from about 20 to about 50 parts.

In non-reactive plasticizer applications, from 15 to 60 wt. % preferablyfrom 20 to 40 wt. %, of the appropriate ester of the cumylphenol is usedbased on total weight of resin.

In the applications of the invention where the cumylphenols are used asreactive diluents or non-reactive plasticizers, the cumylphenol compoundis initially blended with the appropriate resin along with other desiredcomponents. The blend is feeed to the polymerizing reactor and the resinpolymerized in accordance with known techniques for the particularresin.

Where the cumyl phenols are used as reactive diluents for epoxy resins,any known curing system may be used. If an amine system is used, thecumylphenol may also have an accelerating effect; however, other curingsystems, e.g., anhydrides, are fully acceptable.

The resins which are cured and formed in the practice of the invention,with the exception of polyvinyl chloride, may be generally referred toas "liquid thermoset resins." By this term is meant resins which are inthe liquid state under conditions of application and include castingresins, i.e., liquid monomers or incompletely polymerized polymers,usually containing catalysts or curing agents, capable of becoming hardafter they are cast in molds; and coating resins, i.e., liquid monomersor incompletely polymerized polymers, optionally in a solvent ornon-solvent extender, which are capable of application by casting,potting, brushing, rolling, spraying or dipping. These include paints,varnishes, enamels, lacquers, and casting and potting resins.

The resins of particular interest in the instant invention are epoxyresins, furans, phenolics, urethanes and polyvinyl chloride. These maybriefly be described as follows:

A wide variety of epoxy resins are described in U.S. Pat. No. 2,698,315,issued Dec. 28, 1954; U.S. Pat. No. 2,707,708, issued May 3, 1955; andU.S. Pat. 2,705,223, issued Mar. 29, 1955, all of which are incorporatedherein by reference. These resin are commonly complex polymeric reactionproducts of polyhydric alcohols with polyfunctional halohydrins such asepichlorohydrin and glyceryl dichlorohydrin. The products obtained maycontain terminal epoxy groups, or terminal epoxy groups and terminalprimary hydroxyl groups. See, for example, Column 6 of U.S. Pat. No.2,872,428, issued Feb. 3, 1959.

The furan resins are thermosetting resins obtained primarily by thecondensation polymerization of furfural alcohol in the presence of astrong acid, sometimes in combination with formaldehyde or furfural. Theterm also includes resins made by condensing phenol with furfurylalcohol or furfural, and furfuryl-ketone polymers.

Phenolic resins are a family of thermoset resins made by the reaction ofphenols with aldehydes such as formaldehyde, acetaldehyde, or furfuralin the presence of either acidic or basic catalysts. For casting,B-stage resins are generally used. Examples of the phenols are di- andtrivalent phenols such as cresol, resorcinol and cardanol. In castingresin applications, a large excess of formaldehyde is generally usedwith sodium hydroxide as the catalyst. The reaction is usually carriedout at about 64° C.

The polyurethanes are a family of resins produced by reactingdiisocyanates with organic compounds containing two or more active atomsto form polymers having free isocyanate groups. A detailed descriptionof these resins is given in U.S. Pat. No. 3,060,137, issued Oct. 23,1962. These groups, under the influence of heat or catalyst, will reactwith each other or with water, glycols, etc., to form thermosettingmaterials.

Rigid polyvinyl chloride resins optionally contain extenders, pigments,stabilizers and a small proportion of plasticizers wherein theproportion of plasticizer is insufficient to reduce tensile modulusbelow about 2000 psi.

The following two examples show the embodiments of the inventionrelating to the use of cumylphenols as accelerators in amine-cured epoxysystems:

EXAMPLE 1

This example shows the use of a blend of 60% cumylphenol, 34%alpha-methylstyrene dimer and 6% acetophenone as an accelerator for thecure of epoxy resins. The composition has the following properties:

    ______________________________________                                        Specific Gravity at 25° C.                                                                      1.052                                                Viscosity at 25° C., cps                                                                       99                                                    Distillation Range                                                             (5%-95% ASTM D-86), °C.                                                                       236-327                                               Flash Point COC, °F.                                                                           275                                                   Hydroxyl Number         171                                                   Avg. Molecular Weight (Calc.)                                                                         209                                                   Gardner Color           9-10                                                  Pour Point, °F.  Below 40                                              ______________________________________                                    

Tests were performed with Epon 828 (trademark of Shell Chemical Co.), anepoxy resin having an epoxy equivalent of 185 to 192 with two curatives,namely, diethylenetriamine and triethylenetetramine. The admixture ofthe invention was compared to conventional accelerators, namely,nonylphenol and dinonylphenol. The compositions are shown in thefollowing table along with the gel time, cure time, and Shore D hardnessof the cured compositions.

                                      TABLE I                                     __________________________________________________________________________    Compound No.                                                                              1  2  3  4  5  6  7  8                                            __________________________________________________________________________    Epoxy Resin (185-192                                                          Epoxide Equivalent)                                                                       100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                          Diethylenetriamine                                                                        10 -- 10 10 10 -- -- --                                           Triethylenetetramine                                                                      -- 12 -- -- -- 12 12 12                                           Nonylphenol -- -- 20 -- -- 20 -- --                                           Dinonylphenol                                                                             -- -- -- 20 -- -- 20 --                                           Cumylphenol Blend                                                                         -- -- -- -- 20 -- -- 20                                           Gel Time, minutes                                                                         74 68 28 40 28 28 36 24                                           Cure Time, minutes                                                                        158                                                                              150                                                                              107                                                                              125                                                                              112                                                                              98 120                                                                              102                                          Shore D Hardness,                                                             24 hrs. at 20°C.                                                                   85 85 85 82 87 86 80 86                                           __________________________________________________________________________

The above data show that the cumylphenol blend has a superior cure rateas compared with the unaccelerated runs. This material also showssuperiority to the dinonylphenol accelerator but is about 10-20% slowerthan the nonylphenol. Considering the ready availability of theaforesaid blend and the fact that it contains considerably less of thephenolic compound than the pure nonylphenol, its activity as anaccelerator is particularly outstanding.

EXAMPLE 2

Four epoxy resin formulations were prepared, the first without anaccelerator; the second with the prior art accelerator, nonylphenol; andthe last two with different levels of high purity cumylphenol. Thecumylphenol had the following physical properties:

    ______________________________________                                        Appearance: Light tan crystalline material                                    Specific Gravity, 25/25°C.                                                                      1.094                                                Flash Point, COC, °F.                                                                             345                                                Drop Melting Point, °F.                                                                           154                                                ______________________________________                                    

Table II below shows the specific composition of the formulations, thegel and cure times, and the Shore D hardness of the cured material:

                  Table II                                                        ______________________________________                                                      1     2       3       4                                         ______________________________________                                        Epon 828        100     100     100   100                                     Triethylenetetramine                                                                          12      12      12    12                                      Nonylphenol     --      20      --    --                                      Cumylphenol     --      --      20    10                                      Gel Time, min.  68      28       14.5 22                                      Cure Time, min. 150     107     78    96                                      Shore D Hardness,                                                             24 hrs., at 20°C.                                                                      85      85      93    89                                      ______________________________________                                    

The above table not only shows the improved cure and gel times achievedby using the cumylphenol, but it also shows that, at only half the levelof the prior art accelerator, improvement is realized. Furthermore, thecumylphenol, particularly at the level of Formulation No. 4, improvesthe Shore D hardness, a result not realized with the nonylphenol.

The following Examples 3 to 10 illustrate the effectiveness of thecumylphenols as reactive diluents for epoxy, furan, phenolic andurethane resins.

EXAMPLE 3

This example shows the effect of cumylphenol and its derivatives on thephysical properties of epoxy resins. Formulations were prepared usingEpon 828 (average viscosity, 16,000 centipoise) epoxy resins, 100 parts;triethylenetetramine as a curative, 12 parts; and Berkley #1 sand inamounts shown in the following table; and with cumylphenol and itsacetate and glycidyl ether derivatives. The compressive strength and thetensile strength of compositions, cured at ambient temperature, weremeasured after five days. The following table shows the formulations andthe results obtained:

                  Table III                                                       ______________________________________                                                  Parts                Compressive                                                                            Tensile                                         by                   Strength,                                                                              Strength,                             Additive  Weight  Epoxy   Sand psi M    psi M                                 ______________________________________                                         None     --      88      200  12.0     0.9                                   "         --      88      250  10.9     0.76                                  "         --      88      300   9.5     0.71                                  "         --      88      350  NP       NP                                    Cumylphenol                                                                             22      66      200  17.3     1.2                                   "         22      66      250  16.9     1.0                                   "         22      66      300  16.5     0.91                                  "         22      66      350  15.8     0.82                                  "         22      66      400  NP       NP                                    Cumylphenyl                                                                   Acetate   22      66      200  19.4     1.65                                  Cumylpheny                                                                    Acetate   22      66      250  18.1     1.51                                  Cumylphenyl                                                                   Acetate   22      66      300  17.3     1.38                                  Cumylphenyl                                                                   Acetate   22      66      400  14.8     1.16                                  Cumylphenyl                                                                   Acetate   22      66      450  12.1     0.94                                  Cumylphenyl                                                                   Acetate   22      66      500  NP       NP                                    Cumylphenyl                                                                   Glycidyl Ether                                                                          22      66      200  14.6     1.08                                  Cumylphenyl                                                                   Glycidyl Ether                                                                          22      66      250  13.7     0.98                                  Cumylphenyl                                                                   Glycidyl Ether                                                                          22      66      300  12.1     0.92                                  Cumylphenyl                                                                   Glycidyl Ether                                                                          22      66      400   9.9     0.83                                  Cumylphenyl                                                                   Glycidyl Ether                                                                          22      66      450  NP       NP                                    ______________________________________                                         NP = nonpourable                                                         

The above table clearly shows that the compressive strength and thetensile strength are markedly improved by substituting the cumylphenolor its derivatives for a portion of the epoxy composition. The tablefurther shows that 400, 500 and 450 parts were added in the cases of thecumylphenol, the cumylphenyl acetate and the cumylphenyl glycidyl ether,respectively, before the non-pourable condition occurred. This showsthat the additives of the invention all have an effect of reducing theviscosity of the mixture. This is of great advantage, since it permitshigher loading and lower cost compositions.

EXAMPLE 4

Two anhydride cure epoxy resin formulations were prepared, the firstusing a reactive diluent known in the art, cresyl glycidyl ether, andthe second p-cumylphenyl acetate of the invention. The compositions andflexural strength of the product cured for 20 minutes at 375° F. areshown in the table below:

                  Table IV                                                        ______________________________________                                                          1       2                                                   ______________________________________                                        Epoxy 6010          80        80                                              Cresyl glycidyl ether                                                                             20        --                                              p-cumylphenylacetate                                                                              --        20                                              Dodecylsuccinic anhydride                                                                         50        50                                              Flexural strength   13.5 M    20.3 M                                          ______________________________________                                    

The above table shows that in comparison to the reactive diluents of theprior art the acetate ester of cumylphenol results in a product having asubstantially higher flexural strength. Additionally, this example showsthe application of cumylphenol derivatives in anhydride-cured epoxyresins, as well as the amine-cured system shown in Example 3.

EXAMPLE 5

This example shows the effect of p-cumylphenyl acetate on the viscosityof epoxy flooring compounds. A control compound containing 100 parts ofResiplex 1628 (trademark of Resyn Corp. for an epoxy resin having aviscosity of 12,000 cps) was admixed with 20 parts of an acceleratedproprietary aliphatic polyamine hardener (Celanese 874) and 160 parts ofColorquartz #28 (trademark of 3M Co.). Additional compositions wereformulated, the first containing 65 parts of the Resiplex and 35 partsof the p-cumylphenyl acetate, and the second 50 parts each of theResiplex and the p-cumylphenyl acetate. It was found that the sandcontent could be increased to 260 and 300 parts in these compositions,respectively, without adversely affecting the "trowel feel" of thecomposition. Savings are realized not only in increasing the amount offiller present but by using the low cost p-cumylphenyl acetatederivative in place of the expensive epoxy resin.

EXAMPLE 6

This example shows the use of cumylphenyl derivatives as a replacementfor furfuryl alcohol in furfural epoxy systems. Four formulations wereprepared. The first formulation served as a control and represents atypical epoxy-furfural system using a phenyl glycidyl ether-modifiedresin. Formulation 2 is substantially the same as the first, but showsthe use of a less expensive unmodified epoxy resin. Formulations 3 and 4show the application of the instant invention whereby the p-cumylphenylacetate serves to replace the furfuryl alcohol. Table V shows thespecific compositions employed. The viscosity of the formulations andtheir physical properties were tested.

                  Table V                                                         ______________________________________                                        Formulation       1       2       3     4                                     ______________________________________                                        Epoxy 6004*       73      --      --    44                                    Epoxy 6010*       --      73      44    --                                    Furfuryl Alcohol  27      27      --    --                                    p-Cumylphenylacetate                                                                            --      --      29    29                                    Graded Sand (Pre-blended)                                                                       376     376     376   376                                   Methylene dianiline                                                           (Pre-blended)     24      24      24    24                                    ______________________________________                                         *Ciba-Geigy trademark of epoxy resins                                    

Formulation 2 was of little use since it was not pumpable. On the otherhand, Formulation 3 had a viscosity comparable to Formulation 1, andFormulation 4 was even less viscous than the control. Furthermore, thephysical properties, such as hardness, tensile and compressive strength,of Formulations 3 and 4 were all within ±10% of the control, again withFormulation 4 showing a slight edge.

EXAMPLE 7

This example shows the use of the cumylphenol, its derivatives, andblends thereof as a replacement for furfuryl alcohol in a typical furaneresin system. Table VI below shows the compositions tested:

                  Table VI                                                        ______________________________________                                                       1     2        3      4                                        ______________________________________                                        Furfural         40      40       50   40                                     Furfuryl Alcohol 60      --       --   30                                     p-cumylphenylacetate                                                                           --      60       --   --                                     Cumylphenol      --      --       50   --                                     Cumylphenol Blend*                                                                             --      --       --   30                                     Coke Flour       200     200      200  200                                    para-Toluene Sulfonic Acid                                                                      5       9        9    9                                     Sulfamic Acid    tr.     tr.      tr.  tr.                                    Qualitative Properties                                                                                          Very                                        Hardness         Brittle Flexible Hard Hard                                   Impact           Very    Very     Fair Good                                                    Poor    Good                                                 rebound          Poor    Very     Fair Fair                                                            Good                                                 Chemicals        Poor    Good     Very Good                                                                     Good                                        ______________________________________                                         *See Example 1.                                                          

The p-cumylphenylacetate as compared with the furfural-furfuryl alcoholcontrol had improved flexibility as well as impact rebound and chemicalproperties. On the other hand, the cumylphenol provided a very hardmaterial with somewhat improved impact and rebound properties and verygood chemical resistance. Finally, the cumylphenol blend resulted in aharder material with good impact and chemical resistance and improvedrebound properties. Considering the substantially lower cost of thematerials discussed herein, the improved chemical and physicalproperties are particularly surprising. The properties obtained arecomparable to phenolic resins.

Still another advantage is that one can use an unmodified epoxy resin(6010) rather than the phenyl glycidyl ether-modified resin (6004)conventionally used in such coating compositions.

EXAMPLE 8

To show the usefulness of cumylphenyl derivatives for replacing thephenolic component in baking resins, five formulations were prepared.The first consisted of the conventional epoxy phenolic composition; thesecond, third and fourth showed the replacement of 25%, 50% and 75% ofthe phenolic resin with the p-cumylphenylacetate; and the last showedcomplete replacement. The specific compositions are shown in thefollowing table:

                  Table VII                                                       ______________________________________                                        Formulations 1       2       3     4     5                                    ______________________________________                                        Epon 828 Epoxy Resin                                                                       37.5    37.5    37.5  37.5  37.5                                 Bakelite Phenolic                                                             Resin, #BKR-2620                                                                           25.5    19.1    12.7  6.4   --                                   p-cumylphenylacetate                                                                       --      6.4     12.7  19.1  25.5                                 Melamine     25.0    25.0    25.0  25.0  25.0                                 Solvent      220.0   220.0   220.0 220.0 220.0                                ______________________________________                                    

The compounds of the invention, namely, those in Formulations 2 through5, cured and behaved comparably to the control. Where the control had ashelf life of approximately three months, each of these latterformulations had shelf lives exceeding three months with no increase inviscosity observed.

EXAMPLE 9

Part I

This example shows the effect of the addition of cumylphenol as amodifier using a conventional phenolic resin. A basic formulation wasprepared containing the following:

    ______________________________________                                        Phenolic Resin Bakelite,                                                      #BRNA-5345             100 parts                                              Colorquartz #28        300 parts                                              Toluene sulfonic acid  5 parts                                                Hexamethylenetetramine 10 parts                                               ______________________________________                                    

The aforesaid formulation was cured for ten minutes at 375° F. and thetensile strength compared to formulations wherein 10 and 20 parts byweight of furfural:cumylphenol (2:3 dry weight) monomer mixture wereused with 90 and 80 parts, respectively, of the phenolic resin.

Tensile strength on the three cured compositions showed 350, 430 and 490for the unmodified resin, the 90:10 and the 80:20 modified resins,respectively. This clearly shows that the monomer mixture is useful inimproving the physical characteristics of phenolic systems.

Part II

Using the basic formulation described in Part I, various proportions ofthe phenolic resin were replaced by equal weights of the monomermixtures shown below. In each case, the monomer mixture contained 2parts of furfural and 3 parts of phenolic monomer. The tensile strengthof each formulation was tested. The composition of the formulations areshown in the table below.

                  Table VIII                                                      ______________________________________                                        Monomer Mixture Added     Tensile                                             Parts Replaced                                                                          Mixture             Strength, psi                                   ______________________________________                                        --        None                350                                             25        Furfural:cumylphenol                                                                              570                                             50        Furfural:cumylphenol                                                                              730                                             100       Furfural:cumylphenol                                                                              910                                             25        Furfural:cumylphenyl acetate                                                                      380                                             100       Furfural:cumylphenyl acetate                                                                      560                                             25        Furfural:nonylphenol                                                                              380                                             100       Furfural:nonylphenol                                                                              480                                             ______________________________________                                    

The above table shows that the replacement of the phenolic resin by thefurfural cumylphenol monomer mixtures results in continually improvedtensile strength, up to the point where, when the phenolic resin iscompletely replaced, a composition having almost three times the tensilestrength is obtained. In the case of the cumylphenyl acetate, animprovement is noted, but not to as great a degree as with thecumylphenol monomer mixture. In contrast, the use of thefurfural-nonylphenol mixture, a mixture not within the scope of theinstant invention, shows comparatively little improvement in properties.

The use of the monomer mixtures of the invention to replace all or partof the phenolic resins results in advantages other than the mere tensilestrength improvement. For example, these mixtures are more easilyhandled because they are more fluid than the phenolic resin per se.Additionally, the furfural-cumylphenol monomers may be used underconditions where the conventional phenolic resins' constituent monomerscannot because of the latters' high volatility and toxicity.

EXAMPLE 10

This example shows the use of cumylphenyl glycidyl ether as a reactivediluent for polyurethane.

Part I

The cumylphenyl glycidyl ether was prepared as follows: A 3-liter flaskequipped with a mechanical stirrer, thermometer, addition funnel, andexternal heating and cooling devices was charged sequentially with 1liter of benzene, 1 liter of 4.5 wt. % aqueous sodium hydroxide and 1mole of cumylphenol. The cumylphenol benzene dispersion formed aftermixing was cooled o 10°-15° C., mixed and maintained at 10°-15° C.during the addition of 1.1 moles of epichlorohydrin over a four hourperiod. After the addition of the chlorohydrin, the reaction mix waswarmed to 50° C. for 8 hours. The two phases which formed were separatedand the water phase discarded. The organic phase was thrice washed withcold water and the residual organic material fractionated. One hundredninety grams (71 mole %) of a pale yellow oil having a boiling point at5 mm Hg of 258°-263° C. was obtained. The oil had an Epoxide Numberdetermined by MgCl₂ -HCl titration of 3.72 meq/g, while the theoreticalEpoxide Number for cumylphenyl glycidyl ether is 3.73 meq/g.

Part II

Five polyurethane compositions containing 100 parts by weight ofpolyurethane (Adiprene CM, trademark of E. I. DuPont deNemours & Co.), areaction product of diisocyanate and polyalkylene ether glycol, 30 partsof HAF carbon black, 1 part of mercaptobenzothiazole, 4 parts of2,2'-benzothiazyl disulfide, 0.5 part of zinc chloride-2,2'-benzothiazyldisulfide, 0.75 part of sulfur and 0.5 part of cadmium stearate wereprepared. The first formulation contained no plasticizer or reactivediluent. Second, third and fourth formulations were also prepared, thesecontaining dioctyl phthalate (DOP), dioctyl sebecate (DOS) and a heavyaromatic naphtha oil diluent (Sundex 790, a trademark of Sun OilCompany), respectively. The first two of these materials areconventionally known non-reactive plasticizers, while the fourth is areactive plasticizer. To a fifth formulation, 15 parts by weight of thecumylphenyl glycidyl ether (CGE) of the invention was added. Thecompositions were cured for 60 minutes at 140° C., and the physicalproperties tested. The results are shown in the following table:

                  Table IX                                                        ______________________________________                                                     1     2      3      4      5                                     ______________________________________                                        Plasticizer    None    DOP    DOS  Naphtha                                                                              CGE                                 300% Modulus psi                                                                             2850    1900   1750 1700   1810                                Tensile psi    4050    3800   3550 4550   5200                                Elongation at Break %                                                                         420     470    460  540    530                                Hardness Durometer A                                                                          70      62     61   62     67                                 ______________________________________                                    

The above data clearly show that the cumylphenyl glycidyl ether of theinvention was effective in reducing the modulus of the polyurethaneformulation. They further show that it is substantially better than theother plasticizers, since the cured composition has a much bettertensile strength and, of the compositions tested, there is the leastloss of hardness. This combination of properties is particularly useful,as will be readily recognized by one skilled in the art, and mostsurprising and unexpected. Furthermore, even in the case of the naphthaoil, the other reactive diluent, the tensile strength was much better.This may be attributable to the glycidyl ether improving the cure.

The following Examples 11 to 13 show the use of certain cumylphenolderivatives as non-reactive plasticizers for the specified resins.

EXAMPLE 11

This example shows the use of p-cumylphenylacetate as a non-reactiveplasticizer for urethane resin. The following formulations wereprepared:

                  Table X                                                         ______________________________________                                        Formulation     1       2        3     4                                      ______________________________________                                        Polyurethane resin*                                                                            100     100      100   100                                   Dioctyl phthalate                                                                             --       25      --    --                                     Diethyleneglycol                                                              dibenzoate      --      --        25   --                                     p-cumylphenylacetate                                                                          --      --       --     25                                    300% Modulus, psi                                                                             1570    1040     1110  1070                                   Elongation, %    760     920      900   940                                   Tensile, psi    8500    4580     5270  5750                                   ______________________________________                                         *A polytetramethylene ether glycolbased thermoplastic having a Shore A        hardness of 90.                                                          

The above data show that the p-cumylphenylacetate provides a combinationof higher elongation and much higher tensile strength and similarmodulus efficiency as compared with widely known plasticizers forurethanes.

EXAMPLE 12

This example shows the utility of p-cumylphenyl benzoate as a processingaid and lubricant for the extrusion of rigid PVC.

Part I

Cumylphenyl benzoate is prepared in accordance with the followingprocedure: one mole of cumylphenol was dissolved in 600 ml of benzenecontaining 1.2 moles of triethylamine in a 2-liter stirred glass reactorequipped with external heating and cooling devices. The reaction masswas cooled to and maintained at 15°-20° C. during the addition of 1.1moles of benzoyl chloride over a period of 1.5 hours. After completionof addition, the resulting slurry was heated to and maintained at40°-45° C. for 1 hour, and thereafter cooled to ambient temperature andfiltered. The filter cake was washed with 200 ml of toluene and thecombined washings and filtrate distilled to give 214.9 g (68 mole %) ofa pale yellow oil having a boiling point at 0.5 mm Hg of 261°-265° C., aspecific gravity at 55° C. of 1.082, and a viscosity at 55° C. of 215cps. On standing, the oil solidified to form a while solid having amelting point of 43°-46.5° C.

Part II

The following formulations were premixed in a high intensity mixer(Disona) and ambient temperature and extruded through a standard type 4"pipe die at 180°±10° C., at a fixed power input. The physical propertiesof the extrudate and the rate of extrusion are also shown in the tablebelow:

                  Table XI                                                        ______________________________________                                        Formulations          1        2                                              ______________________________________                                        PVC resin*            100      100                                            Triphenyl phosphite                                                           (stabilizer)          0.5      0.5                                            Diphenyl phthalate                                                            (processing aid)      1.0      --                                             Calcium stearate      1.0      1.0                                            Oxidized polyethylene 0.2      --                                             (Allied Chemical Corp. AC 629A)                                               Wax (Hoechst XL165)   1.0      2.2                                            Cumylphenyl benzoate  --       1.0                                            Extrusion Rate, inches/min.                                                                         8"       10.4"                                          Impact Strength, psi  205      210                                            Flexural Strength, psi                                                                              16.2M    19.1M                                          ______________________________________                                         *VC 100, Bordon Chemical trademark for a low to medium molecular weight       resin.                                                                   

The addition of the benzoate ester resulted in a 24% extrusion rateimprovement and an 18% flex strength improvement, without any sacrificeof impact strength. Other experiments show that the benzoate ester isunique in this regard and that similar improvements do not result fromother cumylphenol derivatives.

EXAMPLE 13

This example shows the use of a higher alkyl ester of cumylphenol as anon-reactive plasticizer for polyvinyl chloride.

Part I

Cumylphenyl 2-ethylhexanoate was prepared in accordance with thefollowing procedure: a 2-liter flask equipped with a mechanicalagitator, a ten theoretical plate fractionating column, an automaticreflux splitter pot, vapor thermometers and thermocontrollers, acondenser, receivers, and external heating and cooling devices, wascharged with 2 moles of cumylphenyl acetate, 5 moles of 2-ethylhexanoicacid and 5 grams of 98% sulfuric acid. Heat was supplied externally andthe distillate was collected at a 20:1 reflux ratio at a vaportemperature below 120° C. at atmospheric pressure. A total of 64 cc ofdistillate was collected in 24 hours. The residual pot contents werecooled to ambient temperature and extracted 5 times with 2 liters of 8%sodium bicarbonate dried over anhydrous Na₂ SO₄ and fractionated to give408 g (58 mole %) of a pale yellowish oil. The oil had a boiling pointat 0.2 mm Hg of 252°-257° C., a specific gravity 20/20 of 1.045 and asaponification value of 2.82 meq/g. The cumylphenyl 2-ethylhexanoateester has a theoretical saponification value of 2.85 meq/g.

Part II

To show the efficacy of the 2-ethylhexanoate ester as a plasticizer forflexible polyvinyl chloride, 100 parts of a medium molecular weight PVCresin was admixed with 40 parts by weight of 5 micron calcium carbonate,and 2 parts by weight of Thermozard S stabilizer (a trademark of M & TChemicals, Inc.). Three formulations were prepared. The first contained30 parts by weight of triethylene glycol dibenzoate, the second 30 partsby weight of dioctyl phthalate, and the third 30 parts by weight of thecumylphenyl 2-ethylhexanoate of the invention. The following table showsthe physical properties of the blend after cure:

                  Table XIII                                                      ______________________________________                                                     1       2         3                                              ______________________________________                                        Plasticizer    TGD       DOP       CPE                                        Hardness Shore A                                                              Scale           78        75        76                                        100% Modulus   1550      1320      1350                                       Tensile Strength,                                                             psi            2350      1890      2510                                       % Elongation    290       310       340                                       ______________________________________                                    

The above table clearly shows that the compound of the inventioneffectively reduces the modulus of the formulation. In comparison to theother plasticizers, the 2-ethylhexanoate ester-containing formulationhas the best tensile strength and percent elongation.

We claim:
 1. A polymerizable composition which comprises an admixture offrom 10 to 100 parts by weight of cumylphenyl glycidyl ether or acumylphenyl ester of a carboxylic acid and 100 parts of a urethaneresin.
 2. A polymeric composition which comprises a copolymer ofcumylphenyl glycidyl ether and a polyurethane.
 3. The polymericcomposition of claim 2 wherein from 10 to 200 parts by weight of thecumylphenyl glycidyl ether are present for each 100 parts of thepolyurethane.
 4. The polymeric composition of claim 2 wherein from 20 to50 parts by weight of the cumylphenyl glycidyl ether are present foreach 100 parts of the polyurethane.
 5. A polymeric composition ofpolyurethane containing a plasticizing amount of a carboxylic acid esterof cumylphenol.
 6. The polymeric composition of claim 5 wherein from 15to 60 wt. % of the carboxylic acid ester of cumylphenol, based on totalresin composition, is present.
 7. The polymeric composition of claim 5wherein the ester of cumylphenol is p-cumylphenylacetate.
 8. Thepolymeric composition of claim 5 wherein from 15 to 60 wt. % of theester of cumylphenol, based on the total resin composition, is presentand the ester of cumylphenol is p-cumylphenylacetate.